CN101694059B - Process for preparing PVDF insulation dielectric layer material for sulfuric dielectric capacitor - Google Patents
Process for preparing PVDF insulation dielectric layer material for sulfuric dielectric capacitor Download PDFInfo
- Publication number
- CN101694059B CN101694059B CN2009102333554A CN200910233355A CN101694059B CN 101694059 B CN101694059 B CN 101694059B CN 2009102333554 A CN2009102333554 A CN 2009102333554A CN 200910233355 A CN200910233355 A CN 200910233355A CN 101694059 B CN101694059 B CN 101694059B
- Authority
- CN
- China
- Prior art keywords
- pvdf
- sulfuric
- dielectric layer
- layer material
- weaving cloth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 43
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 33
- 239000003990 capacitor Substances 0.000 title claims abstract description 30
- 238000009413 insulation Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000004744 fabric Substances 0.000 claims description 46
- 238000009941 weaving Methods 0.000 claims description 33
- 230000004048 modification Effects 0.000 claims description 32
- 238000012986 modification Methods 0.000 claims description 32
- 238000009987 spinning Methods 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 12
- 238000005649 metathesis reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 9
- 230000004927 fusion Effects 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 6
- 238000004220 aggregation Methods 0.000 claims description 5
- 230000002776 aggregation Effects 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 238000004166 bioassay Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 230000010148 water-pollination Effects 0.000 abstract description 4
- 238000010559 graft polymerization reaction Methods 0.000 abstract description 3
- 239000004745 nonwoven fabric Substances 0.000 abstract 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- 238000005098 hot rolling Methods 0.000 description 21
- 238000001816 cooling Methods 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
Images
Landscapes
- Nonwoven Fabrics (AREA)
Abstract
The invention discloses a process for preparing a PVDF insulation dielectric layer material for a sulfuric dielectric capacitor, which utilizes a low-temperature plasma graft polymerization technique to enable hydrophilic monomer MAH to be in graft polymerization on the surface of PVDF spunbond filament nonwoven fabric, can improve hydrophily thereof, can increase acid absorption rate and acid maintaining rate, and can meet requirements of insulation dielectric layers of high-temperature high-acid electrolyte capacitors. The process for preparing a PVDF insulation dielectric layer material for a sulfuric dielectric capacitor firstly utilizes a spunbond process to spin the PVDF filament nonwoven fabric, and then improves the hydrophily of the spun PVDF filament nonwoven fabric.
Description
Technical field
The present invention relates to a kind of insulating medium layer preparation methods, more specifically to a kind of preparation method of PVDF insulation dielectric layer material for sulfuric dielectric capacitor.
Background technology
Insulating medium layer is as electrolytic capacitor or battery system vitals, and its main application is the both positive and negative polarity active material that separates capacitor or battery system, avoids the both positive and negative polarity short circuit.In battery operated process, insulating medium layer itself is not participated in electrochemical thermal energy storage process directly.In charging and discharging process, insulating medium layer plays the channeling that the ion in the electrolyte moves smoothly.
When the main electrolyte composition of electrolytic capacitor is sulfuric acid and when at high temperature using, but existing papery can not satisfy application requirements with general macromolecule spacer.The fiber surface polarity of papery insulating medium layer is high, but corrosion resistance against sulfuric acid is poor, especially hot concentrated sulfuric acid.General macromolecule spacer is except perishable under long-term hot concentrated sulfuric acid effect, and their suction acid amount is little, has satisfied not the requirement of the low internal resistance of capacitor.So low internal resistance high temperature uses the concentrated sulfuric acid to make the capacitor insulation dielectric layer of electrolyte, at first must the heat-resisting concentrated sulfuric acid, good wettability also to be arranged simultaneously and inhale acidly, the loss and the capacitance loss of capacitor are little.In addition, have the insulating medium layer of very strong guarantor's acid ability, can electrolyte sulfuric acid solution tightly be adsorbed; For being in the capacitor of working under the motion state, except stable working, even the capacitor shell has crack or hole; Also be unlikely to seepage, to guarantee the safety of other electronic devices and components.
PVDF is a kind of fluoroplastics of excellent performance, can stand the corrosion of multiple medium solutions such as oxidant, acid, alkali, has good chemical stability, is used as chemical industry corrosion resistant apparatus, coating, filler, chemical medium separating and filtering film etc. in a large number.The filament nonwoven cloth of spun-bond process preparation not only has bigger specific area, and intensity is high, and technology is simple, production efficiency is high, adjustability is strong.Therefore, can utilize spun-bond process to prepare the electrolytic capacitor insulating medium layer.But because PVDF is a kind of hydrophobic material, its water contact angle＞90 °, the hydrophily that makes filament nonwoven cloth is relatively poor, it is lower to inhale sour rate, thereby, need to select suitable monomers and method that the spun-bonded continuous yarn non-weaving cloth is carried out hydrophilic modification.
Summary of the invention
The invention solves the deficiency and the problem that exist in the above-mentioned prior art; A kind of preparation method of PVDF insulation dielectric layer material for sulfuric dielectric capacitor is provided; This method adopts the low temperature plasma graft polymerization process with the surface of hydrophilic monomer MAH glycerol polymerization at PVDF spun-bonded continuous yarn non-weaving cloth; Can improve its hydrophily, and then can improve and inhale sour rate and protect sour rate, can reach a high temperature, the requirement of high-strength acidic electrolysis bath capacitor insulation dielectric layer.
The present invention realizes through following technical scheme:
The preparation method of PVDF insulation dielectric layer material for sulfuric dielectric capacitor of the present invention adopts spunbond technology to spin out PVDF filament nonwoven cloth earlier; Filament nonwoven cloth to spinning carries out hydrophilic modification again.
It is following that the preparation method of PVDF insulation dielectric layer material for sulfuric dielectric capacitor of the present invention, its further technical scheme are that described spunbond technology spins out the method step of PVDF filament nonwoven cloth:
Raw material PVDF behind 80～120 ℃ of following constant temperature baking 10～15h, is extruded through filtration 220-280 ℃ of following fusion; The melt of extruding is that the spinnerets of 0.1～0.5mm is with the ejection of the speed of 500～1000m/min through the aperture under 220～280 ℃ temperature; Obtain continuous as-spun fibre; As-spun fibre forms the long filament uniform spreading through air drawing and is becoming on the fibre web; Between long filament, form bonding point through hot pressing roller adhesive effect again, obtain the spun-bonded continuous yarn non-weaving cloth; The preferred molten index of wherein said PVDF raw material be 70～80 (ASTMD-1238,230 ℃, 5kg).
It is following that the preparation method of PVDF insulation dielectric layer material for sulfuric dielectric capacitor of the present invention, its further technical scheme can also be that described filament nonwoven cloth to spinning carries out the method step of hydrophilic modification:
To make earlier and put into plasma reactor filament nonwoven cloth is removed the impurity on surface with acetone after; Extract the air in the plasma reactor with vavuum pump; When vacuum is 3～5Pa, feed residual air in the Ar gas displacement plasma reactor, the Ar gas that uses hydrophilic modifying monomer M AH steam to repeat to replace in the plasma reactor then is MAH atmosphere to guarantee reactor; Adopt the plasma grafting polymeric modification to handle behind the modification non-weaving cloth non-weaving cloth is placed on and soak 10～20h in the pure water, taking out and being placed on temperature is that oven dry promptly obtains PVDF dielectric layer material in 30～50 ℃ the baking oven; Feeding Ar gas to vacuum earlier when further technical scheme is the air in the described use Ar gas metathesis reactor again is 40～50Pa, and then is evacuated to 3～5Pa with vavuum pump, replaces continuously more than 3 times; Further technical scheme can also be that described hydrophilic modification monomer M AH is earlier through the decompression distillation purifying again; Feeding MAH steam to vacuum earlier when further technical scheme can also be the Ar gas in the described use hydrophilic modifying monomer M AH steam repetition metathesis reactor again is 40～50Pa, and then is evacuated to 3～5Pa with vavuum pump, and the displacement number of times is 5～10 times; The power of plasma reactor was 10～40w when further technical scheme can also be described plasma grafting aggregation processing modification non-weaving cloth again; Processing time is 3～9min, and technical scheme further is that its vacuum is 3～15Pa in the described plasma grafting aggregation processing modification non-weaving cloth process.
The invention has the beneficial effects as follows:
1, Kynoar spun-bonded continuous yarn non-weaving cloth of the present invention, it is that the fibre web hot calendering bonding that the PVDF fiber of 10～20 μ m is paved into forms by the average fiber fineness, its mass area ratio is 65～80g/m
2, thickness is 0.15～0.32mm.This spun-bonded continuous yarn non-weaving cloth through modification can be stablized use in (55～125 ℃) temperature range, serviceability temperature wide ranges (thermal contraction is little, and size distortion is little), and can stand the corrosion that concentration is 55% sulfuric acid solution.
2, the non-weaving cloth after the modification is good to the wettability of the electrolyte sulfuric acid solution of 40% concentration, inhales sour rate height, and electrical conductivity is low; Good insulating, intensity is good, and it is strong to protect sour ability; Centrifugal 5min under the rotating speed of 500rpm, guarantor's acid rate 300-400% of prepared insulating medium layer.
Description of drawings
Fig. 1 is the structural representation that spun-bond process prepares PVDF filament nonwoven cloth equipment
Among the figure:
1, hopper 8, spinning chamber
2, screw extruder 9, cooling wind window
3, filtration system 10, air drawing device
4, melt pipe 11, lapper
5, measuring pump 12, air draft system
6, distribution duct 13, hot rolling system
7, filament spinning component 14, winder
The specific embodiment
Below the present invention is described, but the present invention not merely is defined in these embodiment through specific embodiment.
Embodiment 1
As shown in Figure 1; At first the PVDF raw material is sent into the screw extruder 2 from hopper 1 and melt extruded; The temperature of screw extruder 2 is 260 ℃, and material is fully sent into filtration system 3 after the fusion, after this is with the impurity in the material (grading like carbon, ash) filtering; Material gets in the measuring pump 5 through melt pipe 4, and the temperature of measuring pump 5 and distribution duct 6 remains on about 260 ℃.In spinning chamber 8, carry out spinning, the spun silk of filament spinning component 7 forms crystallization growing filament just after cooling wind window 9 is air-cooled.First growing filament is admitted to air drawing device 10 and carries out drawing-off, and draft speed is 3500m/min, and obtaining the fibrousness fineness after the drawing-off is the fiber of 15 μ m.The strand that from air drawing device 10, comes out is delivered to lapper 11 and is carried out lapping; Lapper 11 belows are provided with air draft system 12; The fiber of completing is through autoadhesion or hot rolling system 13 heating and pressurizing hot rollings; The temperature of hot rolling is 60 ℃, sends into winder 14 rollings after the non-weaving cloth cooling that forms after the hot rolling and obtains the spun-bonded non-woven product.It is the 40mm disk that the PVDF spun-bonded continuous yarn non-weaving cloth that makes is cut into diameter,, takes out after the drying to remove the impurity on surface with acetone; Putting into homemade internal diameter is 2.5cm, long in the tubular reactor of 15cm, with the air in the Ar gas metathesis reactor 5 times; The Ar gas that under the air pressure of 3Pa, repeats in the metathesis reactor with MAH steam (is replaced 6 times; Each guarantee that pressure in the reactor is at 40-50pa) be MAH atmosphere to guarantee reactor, using plasma glycerol polymerization MAH carries out surface hydrophilic modification to the non-weaving cloth that makes again, and modification power is 30w; Modification time is 6min; Non-weaving cloth after modification is handled is placed on and soaks 12h in the pure water, and taking out and being placed on temperature is to dry in 50 ℃ the baking oven, yellow goods.Recording the goods tensile strength is 1.6kN/m; Water absorption rate is 680%; Be dipped in 40% the sulfuric acid, inhaling sour rate is 665%; Protecting sour rate (the centrifugal 5min of 500rpm) is 320%; Electrical conductivity is 1.10mS/m; 55% sulfuric acid, 125 ℃ are boiled 2000h, and color is constant basically, and the TENSILE STRENGTH retention rate is 92%.The result of certain capacitor with super capacity installation test 2000h does, capacitance 12000 μ F, leakage current are 300 μ A, and equivalent parallel resistance (ESR) is 0.045m Ω.
As shown in Figure 1; At first the PVDF raw material is sent into the screw extruder 2 from hopper 1 and melt extruded; The temperature of screw extruder 2 is 280 ℃, and material is fully sent into filtration system 3 after the fusion, after this is with the impurity in the material (grading like carbon, ash) filtering; Material gets in the measuring pump 5 through melt pipe 4, and the temperature of measuring pump 5 and distribution duct 6 remains on about 280 ℃.In spinning chamber 8, carry out spinning, the spun silk of filament spinning component 7 forms crystallization growing filament just after cooling wind window 9 is air-cooled.First growing filament is admitted to air drawing device 10 and carries out drawing-off, and draft speed is 4000m/min, and obtaining the fibrousness fineness after the drawing-off is the fiber of 11 μ m.The strand that from air drawing device 10, comes out is delivered to lapper 11 and is carried out lapping; Lapper 11 belows are provided with air draft system 12; The fiber of completing is through autoadhesion or hot rolling system 13 heating and pressurizing hot rollings; The temperature of hot rolling is 60 ℃, sends into winder 14 rollings after the non-weaving cloth cooling that forms after the hot rolling and obtains the spun-bonded non-woven product.It is the 40mm disk that the PVDF spun-bonded continuous yarn non-weaving cloth that makes is cut into diameter,, takes out after the drying to remove the impurity on surface with acetone; Putting into homemade internal diameter is 2.5cm, long in the tubular reactor of 15cm, with the air in the Ar gas metathesis reactor 5 times; The Ar gas that under the air pressure of 3Pa, repeats in the metathesis reactor with MAH steam (is replaced 6 times; Each guarantee that pressure in the reactor is at 40-50pa) be MAH atmosphere to guarantee reactor, using plasma glycerol polymerization MAH carries out surface hydrophilic modification to the non-weaving cloth that makes again, and modification power is 15w; Modification time is 4min; Non-weaving cloth after modification is handled is placed on and soaks 12h in the pure water, and taking out and being placed on temperature is to dry in 50 ℃ the baking oven, faint yellow goods.Recording the goods tensile strength is 1.8kN/m; Water absorption rate is 560%; Be dipped in 40% the sulfuric acid, inhaling sour rate is 550%, protects sour rate and is (the centrifugal 5min of 500rpm) 300%; Electrical conductivity is 1.34mS/m; 55% sulfuric acid, 125 ℃ are boiled 2000h, and color is constant basically, and the TENSILE STRENGTH retention rate is 98%; The result of certain capacitor with super capacity installation test 2000h is capacitance 12000 μ F, leakage current 290 μ A, equivalent parallel resistance (ESR) 0.046m Ω.
As shown in Figure 1; At first the PVDF raw material is sent into the screw extruder 2 from hopper 1 and melt extruded; The temperature of screw extruder 2 is 220 ℃, and material is fully sent into filtration system 3 after the fusion, after this is with the impurity in the material (grading like carbon, ash) filtering; Material gets in the measuring pump 5 through melt pipe 4, and the temperature of measuring pump 5 and distribution duct 6 remains on about 220 ℃.In spinning chamber 8, carry out spinning, the spun silk of filament spinning component 7 forms crystallization growing filament just after cooling wind window 9 is air-cooled.First growing filament is admitted to air drawing device 10 and carries out drawing-off, and draft speed is 3500m/min, and obtaining the fibrousness fineness after the drawing-off is the fiber of 18 μ m.The strand that from air drawing device 10, comes out is delivered to lapper 11 and is carried out lapping; Lapper 11 belows are provided with air draft system 12; The fiber of completing is through autoadhesion or hot rolling system 13 heating and pressurizing hot rollings; The temperature of hot rolling is 60 ℃, sends into winder 14 rollings after the non-weaving cloth cooling that forms after the hot rolling and obtains the spun-bonded non-woven product.It is the 40mm disk that the PVDF spun-bonded continuous yarn non-weaving cloth that makes is cut into diameter,, takes out after the drying to remove the impurity on surface with acetone; Putting into homemade internal diameter is 2.5cm, long in the tubular reactor of 15cm, with the air in the Ar gas metathesis reactor; The Ar gas (replace 5-6 time, guarantee that at every turn pressure in the reactor is at 40-50pa) that under the air pressure of 3Pa, repeats in the metathesis reactor with MAH steam is MAH atmosphere to guarantee reactor, then adopts plasma modification processing non-weaving cloth; The power of the plasma surface modification of being adopted is 20w; Modification time is 5min, and the non-weaving cloth after modification is handled is placed on and soaks 12h in the pure water, and taking out and being placed on temperature is to dry in 50 ℃ the baking oven; It is to dry in 50 ℃ the baking oven that taking-up is placed on temperature, faint yellow goods.Recording the goods tensile strength is 1.8kN/m; Water absorption rate is 735%; Be dipped in 40% the sulfuric acid, inhaling sour rate is 730%, and protecting sour rate (the centrifugal 5min of 500rpm) is 350%; Electrical conductivity is 1.21mS/m, 55% sulfuric acid, and it is constant basically that the 2000h color is boiled in 125 ℃ of acid, and the TENSILE STRENGTH retention rate is 95%; The result of certain capacitor with super capacity installation test 2000h is capacitance 12000 μ F, leakage current 292 μ A, equivalent parallel resistance (ESR) 0.040m Ω.
As shown in Figure 1; At first the PVDF raw material is sent into the screw extruder 2 from hopper 1 and melt extruded; The temperature of screw extruder 2 is 280 ℃, and material is fully sent into filtration system 3 after the fusion, after this is with the impurity in the material (grading like carbon, ash) filtering; Material gets in the measuring pump 5 through melt pipe 4, and the temperature of measuring pump 5 and distribution duct 6 remains on about 220 ℃.In spinning chamber 8, carry out spinning, the spun silk of filament spinning component 7 forms crystallization growing filament just after cooling wind window 9 is air-cooled.First growing filament is admitted to air drawing device 10 and carries out drawing-off, and draft speed is 4000m/min, and obtaining the fibrousness fineness after the drawing-off is the fiber of 11 μ m.The strand that from air drawing device 10, comes out is delivered to lapper 11 and is carried out lapping; Lapper 11 belows are provided with air draft system 12; The fiber of completing is through autoadhesion or hot rolling system 13 heating and pressurizing hot rollings; The temperature of hot rolling is 60 ℃, sends into winder 14 rollings after the non-weaving cloth cooling that forms after the hot rolling and obtains the spun-bonded non-woven product.It is the 35mm disk that the PVDF spun-bonded continuous yarn non-weaving cloth that makes is cut into diameter,, takes out after the drying to remove the impurity on surface with acetone; Putting into homemade internal diameter is 2.5cm, long in the tubular reactor of 15cm, at first with the air in the Ar gas metathesis reactor; The Ar gas that under the air pressure of 4Pa, repeats in the metathesis reactor with MAH steam again (is replaced 5-6 time; Each guarantee that pressure in the reactor is at 40-50pa) be maleic anhydride atmosphere to guarantee reactor, then adopt the plasma modification to handle non-weaving cloth, the power of the plasma surface modification of being adopted is 30w; Modification time is 7min; Non-weaving cloth after modification is handled is placed on and soaks 12h in the pure water, take out to use that to be placed on temperature be to dry in 50 ℃ the baking oven, yellow goods.The tensile strength that records goods is 1.5kN/m; Water absorption rate is 670%; Be dipped in 40% the sulfuric acid, inhaling sour rate is 650%, and protecting sour rate (the centrifugal 5min of 500rpm) is 330%; Electrical conductivity is 1.08mS/m; It is constant basically that 55% sulfuric acid, 125 ℃ of acid boil the 2000h color, and the TENSILE STRENGTH retention rate is 97%; The result of certain capacitor with super capacity installation test 2000h is capacitance 12000 μ F, leakage current 297 μ A, equivalent parallel resistance (ESR) 0.045m Ω.
As shown in Figure 1; At first the PVDF raw material is sent into the screw extruder 2 from hopper 1 and melt extruded; The temperature of screw extruder 2 is 220 ℃, and material is fully sent into filtration system 3 after the fusion, after this is with the impurity in the material (grading like carbon, ash) filtering; Material gets in the measuring pump 5 through melt pipe 4, and the temperature of measuring pump 5 and distribution duct 6 remains on about 220 ℃.In spinning chamber 8, carry out spinning, the spun silk of filament spinning component 7 forms crystallization growing filament just after cooling wind window 9 is air-cooled.First growing filament is admitted to air drawing device 10 and carries out drawing-off, and draft speed is 3500m/min, and obtaining the fibrousness fineness after the drawing-off is the fiber of 18 μ m.The strand that from air drawing device 10, comes out is delivered to lapper 11 and is carried out lapping; Lapper 11 belows are provided with air draft system 12; The fiber of completing is through autoadhesion or hot rolling system 13 heating and pressurizing hot rollings; The temperature of hot rolling is 60 ℃, sends into winder 14 rollings after the non-weaving cloth cooling that forms after the hot rolling and obtains the spun-bonded non-woven product.It is the 40mm disk that the PVDF spun-bonded continuous yarn non-weaving cloth that makes is cut into diameter, and to be placed on temperature be to dry in 50 ℃ the baking oven to remove the impurity on surface, to take out with acetone, white goods.Recording the goods tensile strength is 2.0kN/m; Water absorption rate is 30%; Be dipped in 40% the sulfuric acid, inhaling sour rate is 16%, and protecting sour rate (the centrifugal 5min of 500rpm) is 5%; Electrical conductivity is 1.21mS/m; It is constant basically that 55% sulfuric acid, 125 ℃ of acid boil the 2000h color, and the TENSILE STRENGTH retention rate is 95%.
Claims (6)
1. the preparation method of a PVDF insulation dielectric layer material for sulfuric dielectric capacitor is characterized in that: adopt spunbond technology to spin out PVDF filament nonwoven cloth earlier; Filament nonwoven cloth to spinning carries out hydrophilic modification again, and the method step that wherein said filament nonwoven cloth to spinning carries out hydrophilic modification is following:
To make earlier and put into plasma reactor filament nonwoven cloth is removed the impurity on surface with acetone after; Extract the air in the plasma reactor with vavuum pump; When vacuum is 3～5Pa, feed residual air in the Ar gas displacement plasma reactor, the Ar gas that uses hydrophilic modifying monomer M AH steam to repeat to replace in the plasma reactor then is MAH atmosphere to guarantee plasma reactor; Adopt behind the plasma grafting aggregation processing modification non-weaving cloth non-weaving cloth is placed on and soak 10～20h in the pure water, taking out and being placed on temperature is that oven dry promptly obtains PVDF dielectric layer material in 30～50 ℃ the baking oven; The power of plasma reactor is 10～40w during described plasma grafting aggregation processing modification non-weaving cloth, and the processing time is 3～9min, and described hydrophilic modification monomer M AH is earlier through the decompression distillation purifying.
2. the preparation method of PVDF insulation dielectric layer material for sulfuric dielectric capacitor according to claim 1, it is following to it is characterized in that described spunbond technology spins out the method step of PVDF filament nonwoven cloth:
Raw material PVDF behind 80～120 ℃ of following constant temperature baking 10～15h, is extruded through filtration 220-280 ℃ of following fusion; The melt of extruding is that the spinnerets of 0.1～0.5mm is with the ejection of the speed of 500～1000m/min through the aperture under 220～280 ℃ temperature; Obtain continuous as-spun fibre; As-spun fibre forms the long filament uniform spreading through air drawing and is becoming on the fibre web; Between long filament, form bonding point through hot pressing roller adhesive effect again, obtain the spun-bonded continuous yarn non-weaving cloth.
3. the preparation method of PVDF insulation dielectric layer material for sulfuric dielectric capacitor according to claim 2; The melt index that it is characterized in that described PVDF raw material is 70～80, and the bioassay standard of this melt index and condition are: ASTMD-1238,230 ℃, 5kg.
4. the preparation method of PVDF insulation dielectric layer material for sulfuric dielectric capacitor according to claim 1; Feeding Ar gas to vacuum earlier when it is characterized in that the air in the described use Ar gas metathesis reactor is 40～50Pa; And then be evacuated to 3～5Pa with vavuum pump, replace continuously more than 3 times.
5. the preparation method of PVDF insulation dielectric layer material for sulfuric dielectric capacitor according to claim 1; It is characterized in that feeding MAH steam to vacuum earlier when described use hydrophilic modifying monomer M AH steam repeats the Ar gas in the metathesis reactor is 40～50Pa; And then being evacuated to 3～5Pa with vavuum pump, the displacement number of times is 5～10 times.
6. the preparation method of PVDF insulation dielectric layer material for sulfuric dielectric capacitor according to claim 1 is characterized in that its vacuum is 3～15Pa in the described plasma grafting aggregation processing modification non-weaving cloth process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102333554A CN101694059B (en) | 2009-10-20 | 2009-10-20 | Process for preparing PVDF insulation dielectric layer material for sulfuric dielectric capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102333554A CN101694059B (en) | 2009-10-20 | 2009-10-20 | Process for preparing PVDF insulation dielectric layer material for sulfuric dielectric capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101694059A CN101694059A (en) | 2010-04-14 |
| CN101694059B true CN101694059B (en) | 2012-02-29 |
Family
ID=42093052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102333554A Expired - Fee Related CN101694059B (en) | 2009-10-20 | 2009-10-20 | Process for preparing PVDF insulation dielectric layer material for sulfuric dielectric capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101694059B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114575041A (en) * | 2022-03-01 | 2022-06-03 | 浙江盛纺纳米材料科技有限公司 | Hydrophilic spun-bonded nonwoven fabric, preparation method thereof and hydrophilic silk thread |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205305A (en) * | 2007-12-05 | 2008-06-25 | 天津工业大学 | Negative electric charge polyvinylidene fluoride modified film and preparation thereof |
| CN101463140A (en) * | 2009-01-14 | 2009-06-24 | 天津工业大学 | Preparation of ultra-hydrophobic polyvinylidene fluoride membrane and product thereof |
-
2009
- 2009-10-20 CN CN2009102333554A patent/CN101694059B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205305A (en) * | 2007-12-05 | 2008-06-25 | 天津工业大学 | Negative electric charge polyvinylidene fluoride modified film and preparation thereof |
| CN101463140A (en) * | 2009-01-14 | 2009-06-24 | 天津工业大学 | Preparation of ultra-hydrophobic polyvinylidene fluoride membrane and product thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴淼等.马来酸酐等离子体改性聚丙烯薄膜表面的硫酸腐蚀行为.《腐蚀与防护》.2009,第30卷(第1期),第25-28页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101694059A (en) | 2010-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | A review of electrospun nanofiber-based separators for rechargeable lithium-ion batteries | |
| Zhang et al. | Poly (vinylidene fluoride)/SiO2 composite membranes prepared by electrospinning and their excellent properties for nonwoven separators for lithium-ion batteries | |
| Miao et al. | Electrospun polyimide nanofiber-based nonwoven separators for lithium-ion batteries | |
| Choi et al. | Electrospun PVDF nanofiber web as polymer electrolyte or separator | |
| Chen et al. | Improved performance of PVdF-HFP/PI nanofiber membrane for lithium ion battery separator prepared by a bicomponent cross-electrospinning method | |
| CN102242464B (en) | Polymer-ceramic compound nanometer fibrous membrane as well as preparation method and application thereof | |
| CN104766938B (en) | A kind of compound lithium ion battery separator and preparation method thereof | |
| CN102629679B (en) | Nanofiber lithium ion battery separator material with composite construction and preparation method thereof | |
| Dong et al. | Surface-modified electrospun polyacrylonitrile nano-membrane for a lithium-ion battery separator based on phase separation mechanism | |
| CN104157815B (en) | A kind of Bacterial cellulose porous membrane and preparation method thereof | |
| US20100304205A1 (en) | Heat resisting separator having ultrafine fibrous layer and secondary battery having the same | |
| KR101432862B1 (en) | Porous support and method for manufacturing the same | |
| JP6686141B2 (en) | Composite film, method for producing the same, and lithium battery having the same | |
| Xiao et al. | PVA-ZrO2 multilayer composite separator with enhanced electrolyte property and mechanical strength for lithium-ion batteries | |
| CN104466063B (en) | Poly-dopamine surface modification polyether sulfone nanofiber composite diaphragm, preparation method and application | |
| WO2008018656A1 (en) | Heat resisting ultrafine fibrous separator and secondary battery using the same | |
| JP2013510389A (en) | Heat resistance, high-strength ultrafine fiber separation membrane, method for producing the same, and secondary battery using the same | |
| CN110158200A (en) | Porous carbon nanofiber and preparation method thereof and lithium-sulfur cell | |
| CN104309232B (en) | Acid-resisting and alkali-resisting porous film enhanced by polyimide nanofiber and preparation method and application of porous film | |
| CN108285643A (en) | Cellulose nano-fibrous/the Sulfonated Polyethersulfone Proton Exchange Membrane of one kind and preparation method | |
| CN108335917A (en) | A kind of preparation method of carbon nanofibers load ordered arrangement redox graphene electrode material | |
| CN109841899A (en) | A kind of preparation method of the three-dimensional network gel-form solid polymer electrolyte film based on bacteria cellulose | |
| Zou et al. | Lithium-ion battery separators based-on nanolayer co-extrusion prepared polypropylene nanobelts reinforced cellulose | |
| Zhao et al. | A novel cellulose membrane from cattail fibers as separator for Li-ion batteries | |
| CN101694812B (en) | Process for preparing porous fiber membrane for high-temperature-resistant high-acid electrolyte capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120229 Termination date: 20201020 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |